TW202146362A - Stabilized urea containing fertilizer blends - Google Patents

Abstract

A fertilizer blend containing 10 wt. % to 90 wt. % of a first particulate fertilizer composition and 10 wt. % to 90 wt. % of a second particulate fertilizer composition is disclosed. In the fertilizer blend, the second particulate fertilizer composition can be blended with the first particulate fertilizer composition. The first particulate fertilizer composition can include a core containing a binder, a pH buffering agent, and an urease inhibitor, and a shell containing urea, where the shell covers at least a portion of an outer surface of the core.

Description

Stabilized urea-containing fertilizer blend

The present invention generally relates to fertilizer blends comprising 10% to 90% by weight of a first granular fertilizer composition containing urea and 10% to 90% by weight of a second granular fertilizer composition. In particular, the first granular fertilizer composition may comprise a granule having a core shell structure, and the core contains a binder, a pH buffer and a urease inhibitor, and the shell contains urea.

To increase crop yields and meet the demands of a growing population, more fertilizers are being used in agriculture. However, continued use of fertilizers can lead to nutrient imbalances and loss of soil fertility. For example, urea fertilizers are widely used, which can cause degradation of soil health and other environmental problems (such as greenhouse gas emissions and groundwater pollution) due to their rapid hydrolysis in soil by soil bacteria.

Hydrolysis of urea in soil can be counteracted by adding urease inhibitors to the fertilizer. Urease inhibitors reduce the amount of hydrolyzed urea, which reduces the amount of nitrogen lost through ammonia volatilization. Although the use of urease inhibitors in fertilizers has been used as a solution to the problem of urea hydrolysis, certain difficulties still exist when using such inhibitors. One problem is that some urease inhibitors are heat and moisture sensitive and can also decompose during storage. While attempts have been made to produce fertilizer compositions with stabilized urease inhibitors, such attempts may pose additional problems and fail to address the aforementioned problems associated with urease inhibitor degradation. For example, WO2017100507A1 discloses the use of alkaline components to improve urease inhibitor storage. One of the potential problems with using alkaline components is that they can affect soil pH and adversely affect soil health.

Solutions to at least some of the problems discussed above have been found. In one aspect, it was found that, in some cases, urease inhibitors such as N-(n-butyl) triamide thiophosphate (NBPT), in addition to being sensitive to heat and moisture, can be used in addition to urea Degrades in the presence of external plant fertilizers. A solution to this degradation problem was found. In one aspect, the solution is to provide a fertilizer blend containing at least two different particle fertilizer compositions. The fertilizer blend may contain, i) a first granular fertilizer composition containing core-shell fertilizer granules having a core containing a urease inhibitor, and a shell containing urea, wherein the shell covers the outside of the core at least a portion of the surface, and ii) a second granular fertilizer composition containing additional plant fertilizer other than urea. Without wishing to be bound by theory, providing the additional fertilizer as a separate granular composition and further separating the urease inhibitor in the core from the additional fertilizer by the outer shell may help stabilize the urease inhibitor and/or reduce urease Inhibitor degradation.

One aspect of the present invention pertains to a fertilizer blend comprising a first granular fertilizer composition and a second granular fertilizer composition, wherein the second granular fertilizer composition can be blended with the first granular fertilizer composition. Based on the total weight of the fertilizer blend, the fertilizer blend may include 10% to 90% by weight of the first granular fertilizer composition and 10% to 90% by weight of the second granular fertilizer composition. In some aspects, the fertilizer admixture is storage stable for longer periods of time than some other fertilizer admixtures. In some cases, the fertilizer blend retains temperature and/or moisture sensitive components at more than 40% of the original concentration for more than 14 days when stored under indoor conditions. In some cases, the fertilizer blend retains some of the temperature and/or moisture sensitive components for more than 60 days when stored under indoor conditions. In some cases, the fertilizer blend retains temperature and/or moisture sensitive components at more than 40% of the original concentration for more than 1 day when stored at 40 ± 2°C and 75 ± 5% relative humidity, respectively. In some cases, the fertilizer blend retains some of the temperature and/or moisture sensitive components for more than 15 days when stored at 40 ± 2°C and 75 ± 5% relative humidity. In some cases, the temperature and/or moisture sensitive ingredient is a urease inhibitor. In some cases, the urease inhibitor is NBPT.

The first granular fertilizer composition may contain granules having a core-shell structure, and the core contains a binder, a pH buffer, and a urease inhibitor, and the shell contains urea, wherein the shell covers at least a portion of the outer surface of the core . In some aspects, the outer shell may contain 50 to 100 wt %, preferably 85 to 100 wt % urea, based on the total weight of the outer shell. In one instance, the shell does not include any other fertilizers other than urea (eg, (MAP), diammonium phosphate (DAP), potassium chloride (MOP), potassium dihydrogen phosphate (MKP), triple superphosphate ( TSP), phosphate rock, monosuperphosphate (SSP), etc.). In some aspects, the shell consists essentially of or consists of urea. The shell may comprise 70 to 99%, preferably 90 to 97%, or about 95% by weight of the total weight of the first granular fertilizer composition, and the core may comprise the total weight of the first granular fertilizer composition 1 to 30% by weight, preferably 3 to 10% by weight, 3 to 7% by weight, or about 5% by weight.

In some aspects, the binder can include plaster of paris, flour, chalk, bleached wheat flour, starch, gluten, kaolin, bentonite, or colloidal silica or any combination thereof, preferably plaster of paris, and/or bleached wheat flour . In some aspects, the core may contain from 10% to 95% by weight, preferably from 25% to 65% by weight, of a binder (such as plaster of paris and/or bleached wheat flour) based on the total weight of the core. In some aspects, pH buffers may _{CaCO 3, Na 2 CO 3,} K 2 CO 3, MgO, KH 2 PO 4, NaHCO 3 or MgCO _3, or any combination thereof, preferably CaCO _3. In some aspects, the chalk CaCO ₃ as included in the core. In some aspects, the core may contain from 5% to 60% by weight, preferably from 30% to 55% by weight, of a pH buffer (such as chalk) based on the total weight of the core.

In some aspects, the urease inhibitor can include a triamide phosphorothioate derivative, preferably N-(n-butyl) phosphorothioate triamide (NBPT). In some aspects, the core can include 1% to 5% by weight of a urease inhibitor (such as NBPT) based on the total weight of the core.

The core may optionally contain a plasticizer. In some aspects, the plasticizer can have a melting point greater than 150°C. In some aspects, the plasticizer can contain hydroxypropyl methylcellulose (HPMC), carboxymethylcellulose, polyethylene glycol (PEG), guar gum, locust bean gum, xanthan gum, natural Gum, lignosulfonate or hydroxyethyl cellulose or any combination thereof, preferably HPMC. In some aspects, the core may contain 0.01 wt% to 5 wt% of a plasticizer (such as HPMC) based on the total weight of the core.

The core and/or shell may optionally contain nitrification inhibitors. In some aspects, the nitration inhibitor can contain dimethylpyrazole 3,4-phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl) )-pyridine (Nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (Terrazole), 2-amino-4- Chloro-6-methyl-pyrimidine (AM), 2-mercapto-benzothiazole (MBT) or 2-sulfathiazole (ST), or any combination thereof, preferably DCD. In some specific aspects, the core can contain 10% to 30% by weight of a nitrification inhibitor (such as DCD) based on the total weight of the core.

The core can optionally contain filler. In some aspects, the filler may contain silica, distillers dried grains and their solubles (DDGS), MgO, CaO, bone flour, chalk, rice husks, or any combination thereof. In some aspects, the core of a pH buffer (such as CaCO ₃₎ as a pH buffering agents in addition to its functions, also serve as a filler. In some aspects, the core may contain 1 wt% to 60 wt% filler.

The second granular fertilizer composition may contain plant fertilizers other than urea. In some aspects, the second granular fertilizer composition can contain ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), triple superphosphate (TSP), rock phosphate , monosuperphosphate (SSP), potassium phosphate fertilizers, or any combination thereof. In some aspects, the potassium phosphate fertilizer can be potassium dihydrogen phosphate (MKP). In some aspects, the second granular fertilizer composition can further comprise urea.

In some specific aspects, the second granular fertilizer composition can contain MAP. In some cases, the fertilizer blend may contain 30 to 70 wt% of the first granular fertilizer composition, and 30 to 70 wt% of MAP, based on the total weight of the fertilizer blend. The first granular fertilizer composition may include core-shell particles, and the core contains 30-50 wt% plaster of paris, 5-20 wt% bleached wheat flour, 30 wt% based on the total weight of the core To 55 wt% of a pH buffer (such as chalk), 1 to 5 wt% of a urease inhibitor (such as NBPT), 0.01 to 2 wt% of a plasticizer (such as HPMC), and based on the shell The shell contains 90% to 100% urea by weight of the total weight.

In some specific aspects, the second granular fertilizer composition can contain MAP and MOP. In some cases, based on the total weight of the fertilizer blend, the fertilizer blend can contain 10% to 50% by weight of the first granular fertilizer composition, 30% to 70% by weight MAP, and 5% by weight to 50 wt% MOP. The first granular fertilizer composition may include core-shell particles, and the core contains 30-50 wt% plaster of paris, 5-20 wt% bleached wheat flour, 30 wt% based on the total weight of the core To 55 wt% of a pH buffer (such as chalk), 1 to 5 wt% of a urease inhibitor (such as NBPT), 0.01 to 2 wt% of a plasticizer (such as HPMC), and based on the shell The shell contains 90% to 100% urea by weight of the total weight.

In some specific aspects, the second granular fertilizer composition can contain ammonium sulfate. In some cases, the fertilizer blend may contain 50% to 90% by weight of the first granular fertilizer composition, and 10% to 50% by weight ammonium sulfate, based on the total weight of the fertilizer blend. The first granular fertilizer composition may include core-shell particles, and the core comprises, based on the total weight of the core, 30 to 50 wt% plaster of paris, 5 to 20 wt% bleached wheat flour, 30 to 20 wt% 55 wt% pH buffer (such as chalk), 1 wt% to 5 wt% urease inhibitor (such as NBPT), 0.01 wt% to 2 wt% plasticizer (such as HPMC), and shell-based The shell contains 90% to 100% by weight of urea, based on the total weight.

In some aspects, the fertilizer blend loses less than 60 wt% urease inhibitor after 14 days of storage at ambient conditions. In some aspects, the amount of urease inhibitor lost in the fertilizer blend after 14 days of storage at ambient conditions is less than 60, 59, 58, 57, 56, 55, 54, 53, 52, 51 , 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26 , 25, 24, 23, 22, or 21 wt %, or between any of those values.

The core of the core-shell particle can have any suitable shape, non-limiting shapes including spherical, cubic, cylindrical, puck-shaped, oval, and rectangular. In some aspects, the core can be cylindrical with a circular, oval, oval, triangular, square, rectangular, pentagonal, or hexagonal cross-section, although other shapes of cross-sections can also be fabricated Cylindrical core. In some aspects, the core may have dimensions such as length, width, height, and/or cross-sectional diameter between 0.5 mm and 2.5 mm. In some aspects, the core may have a generally cylindrical shape, with a cylinder having a length of 0.5 mm to 2 mm, or 0.7 mm to 1.6 mm, and a circular cross-sectional diameter of 0.5 mm to 1.5 mm, or 0.8 mm mm to 1.2 mm, where the cross-section is taken along a plane perpendicular to the length of the cylinder. In some aspects, the shell can be formed with a skin layer having a thickness of 0.1 mm to 8 mm, or 1 mm to 6 mm, or 2 mm to 4 mm, on at least a portion of the outer surface of the core. The core-shell particles of the first particle composition can also have various shapes and sizes. Non-limiting shapes of such core-shell particles include spherical, cylindrical, puck-shaped, elliptical, or rectangular. In some aspects, the core-shell particles can have a longest dimension of 1 to 8 mm. In certain aspects, the core can have a generally cylindrical shape with a length of 0.7 mm to 1.6 mm and a generally circular cross-section with a diameter of 0.8 mm to 1.2 mm, and the shell can form a skin on the outer surface of the core At least a portion of, and the core-shell fertilizer particles may have a generally spherical shape with a diameter of 1 mm to 5 mm, 1 mm to 4 mm, 2 mm to 5 mm, or 2 mm to 4 mm. The core may comprise 1 to 10 wt %, preferably 3 to 7 wt %, or about 5 wt % of the total weight of a core-shell particle or a plurality of core-shell particles.

In some aspects, the shell can cover at least 10%, 20%, 30%, 40%, or 10 to 50% of the outer surface of the core. In other aspects, the shell can cover a substantial portion (eg, greater than 50%) of the outer surface of the core. In some aspects, the shell can cover more than 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% of the outer surface of the core. In certain aspects, the shell may cover 60% to 100% or 80% to 100% or 90% to 100% of the outer surface of the core. In some aspects, the weight ratio of shell to core in the core-shell fertilizer granules may be from about 2:1 to 9:1. In some aspects, the shell can comprise about 85% to 95% of the total weight of the core-shell particle. In other aspects, the core may comprise about 5% to 15% of the total weight of the core-shell particle. In some aspects, the core can be a pelletized, compacted and/or agglomerated core. In some aspects, the shell can contain a solidified aqueous urea melt coated on at least a portion of the outer surface of the core. The shell may comprise 70 to 99 wt %, preferably 90 to 97 wt %, or about 95 wt % of the total weight of a core-shell particle or a plurality of core-shell particles.

The second granular fertilizer composition may contain particles of various shapes and sizes. Non-limiting shapes of the particles of the second granular fertilizer composition include spherical, cylindrical, puck, oval or rectangular. The particles of the second granular fertilizer composition may be larger, smaller and/or the same size than the core-shell particles of the first granular fertilizer composition. In some aspects, the second granular fertilizer composition particles can have a longest dimension of 1 to 8 mm. In some specific aspects, the second granular fertilizer particles can have a generally spherical shape with a diameter of 1 mm to 5 mm, 1 mm to 4 mm, 2 mm to 5 mm, or 2 mm to 4 mm.

One aspect of the present invention pertains to a method of making a fertilizer blend and/or increasing the storage stability of a fertilizer containing a urease inhibitor. The methods may include forming and/or providing a first granular fertilizer composition, forming and/or providing a second granular fertilizer composition and having the first granular fertilizer composition and the second granular fertilizer composition in a weight ratio of 1: 9 to 9:1 contact to form a blend of the first granular fertilizer composition and the second granular fertilizer composition. The first granular fertilizer composition and the second granular fertilizer composition may be admixed by methods known in the art (eg, mixing or stirring the first and second compositions together, eg, mixing The first and the second compositions are dry blended to obtain a dry mix comprising the first and second granular fertilizer compositions). The first granular fertilizer composition can be formed by forming a core having an outer surface, contacting at least a portion of the outer surface of the core with a urea-containing solution or urea melt, and cooling and/or drying outside the core The urea solution or urea melt in contact with the surface forms a shell. In some aspects, the core may contain a combination of binders, pH buffers, urease inhibitors, and optionally plasticizers, nitrification inhibitors, and/or fillers by granulation, compaction, and/or granulation matter formation. In some aspects, the contacting of the urea solution or urea melt with at least a portion of the outer surface of the core can include spraying the urea solution or urea melt on the outer surface of the core at a temperature of 110°C to 140°C at least part of it. In some specific aspects, the contacting of the urea solution or urea melt with at least a portion of the outer surface of the core can be performed in a granulator at bed temperature during the contacting process at 80°C to 110°C. In some aspects, the urea solution can be an aqueous urea solution (eg, a 90-96 wt% urea solution in water). In some aspects, the urea solution can be an aqueous solution containing a urea melt. In some aspects, such as compared to some other blends, the method increases the amount of temperature and/or moisture sensitive components in the blend that are retained over time. In some cases, the temperature and/or moisture sensitive ingredient is a urease inhibitor. In some cases, the urease inhibitor is NBPT.

One aspect of the present invention pertains to a method of fertilizing, the method comprising applying a fertilizer blend to soil, a crop, or at least a portion of the soil and the crop. The composition of the present invention stabilizes the urease inhibitor in the fertilizer blend, which relatively reduces the nitrogen loss due to hydrolysis that would otherwise occur. Also disclosed herein is a method of enhancing plant growth comprising applying an effective amount of a composition comprising a fertilizer blend of the present invention to soil, plants, or both soil and plants.

"Core-shell particles" and/or "particles having a core-shell structure" include particles comprising a core and a shell in contact with and covering at least a portion of the outer surface of the core. In the context of the present invention, fertilizer admixture granules, such as the core-shell granules of the first granular fertilizer composition and/or the granules of the second granular fertilizer composition, may also be referred to as granules, granules, fertilizer granules, Small grains, or fertilizer small grains. In some aspects, the core-shell particle can contain a single core. In some aspects, the core-shell particle can contain more than one core, and the shell can cover at least a portion of the outer surfaces of the cores. In certain aspects, the number of cores in the core-shell particles of the first granular fertilizer composition can vary between core-shell particles. In certain aspects, the number of cores in the core-shell particles of the first granular fertilizer composition does not vary, eg, each core-shell particle in the first granular fertilizer composition may contain a single core.

The terms "about" or "approximately" as used herein are defined as close to the meaning as understood by those of ordinary skill. In one non-limiting example, the term is defined within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

The terms "wt %," "vol %," or "mol %" refer to the weight, volume, or mole percent of a component, respectively, based on the total weight, volume, or total moles, respectively, of the materials including the combination. In a non-limiting example, 10 grams of a component in 100 grams of material is a 10 wt% component.

The term "substantially" and variations thereof are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

The terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms, when used in the scope and/or specification of a claim, include any measurable reduction used to achieve a desired result or completely suppressed.

When the term "effective" is used in the specification and/or the scope of the claims, the term "effective" means sufficient to achieve a desired, expected or expected result.

When the word "a" or "an" is used in conjunction with any of the terms "comprising," "including," "containing," or "having," in the scope of a patent application or specification, it may mean "an", but It also complies with the meanings of "one or more", "at least one" and "one or more than one".

The phrase "and/or" may include "and" or "or". For illustration, A, B, and/or C may include: A only, B only, C only, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C.

The wording "comprising" (and any form of comprising, such as "comprise and comprises", "having" (and any form of having, such as "have and has" )"), "including" (and any form of including, such as "includes and include"), or "containing" (and any form of containing, such as "containing" (contains and "contains") are inclusive or open ended and do not exclude additional, unrecited element method steps.

In the context of the present invention, at least the following 20 aspects are described. Aspect 1 relates to a fertilizer blend comprising: 10% to 90% by weight of a first granular fertilizer composition comprising a core and a shell, the core comprising a binder, a pH buffer, and a urease inhibitor, and The outer shell comprises urea, wherein the outer shell covers at least a portion of the outer surface of the core; and 10% to 90% by weight of a second granular fertilizer composition, wherein the second granular fertilizer composition is combined with the first granular fertilizer composition blend. Aspect 2 relates to the fertilizer blend of Aspect 1, wherein the second granular fertilizer composition comprises ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), dihydrogen phosphate Potassium (MKP), triple superphosphate (TSP), rock phosphate, single superphosphate (SSP), or any combination thereof. Aspect 3 relates to the fertilizer blend of any one of Aspects 1 or 2, wherein the second granular fertilizer composition comprises MAP and MOP, and the fertilizer blend comprises 10% to 50% by weight of the first A granular fertilizer composition, 30% to 70% by weight MAP and 5% to 50% by weight MOP. Aspect 4 relates to the fertilizer blend of any one of Aspects 1 or 2, wherein the second granular fertilizer composition comprises MAP, and the fertilizer blend comprises 30% to 70% by weight of the first granules A fertilizer composition, and 30% to 70% MAP by weight. Aspect 5 relates to the fertilizer admixture of any one of Aspects 1 or 2, wherein the second granular fertilizer composition comprises ammonium sulfate, and the fertilizer admixture comprises 50% to 90% by weight of the first Granular fertilizer composition, and 10% to 50% by weight of ammonium sulfate. Aspect 6 relates to the fertilizer blend of any one of Aspects 1 to 5, wherein the binder comprises plaster of paris, flour, bleached wheat flour, starch, gluten, kaolin, bentonite, or colloidal silica, or any combination thereof , preferably plaster of paris and/or bleached wheat flour. 7 based on aspect aspect fertilizer blend of any one of 1 to 6, wherein the pH buffer comprises _{CaCO 3, Na 2 CO 3,} K 2 CO 3, MgO, KH 2 PO 4, NaHCO 3 or MgCO _3, or any combination thereof, preferably CaCO _3. Aspect 8 relates to the fertilizer blend of any one of Aspects 1 to 7, wherein the urease inhibitor comprises a triamide thiophosphate derivative, preferably N-(n-butyl) triamide thiophosphate Amine (NBPT). Aspect 9 relates to the fertilizer blend of any one of Aspects 1-8, wherein the binder is present in the core in an amount of 10% to 95% by weight, based on the total weight of the core. Aspect 10 relates to the fertilizer blend of any one of Aspects 1-9, wherein the pH buffer is present in the core in an amount of 5% to 60% by weight, based on the total weight of the core. Aspect 11 relates to the fertilizer blend of any one of Aspects 1-10, wherein the urease inhibitor is present in the core in an amount of 1 to 5 wt% based on the total weight of the core. Aspect 12 relates to the fertilizer blend of any one of Aspects 1 to 11, wherein the outer shell comprises 50 to 100 wt %, preferably 85 to 100 wt % urea, based on the total weight of the outer shell. Aspect 13 relates to the fertilizer blend of any one of Aspects 1-12, wherein the core further comprises a nitrification inhibitor. Aspect 14 relates to the fertilizer blend of Aspect 13, wherein the nitrification inhibitor is present in the core in an amount of 10% to 30% by weight, based on the total weight of the core. Aspect 15 relates to the fertilizer blend of any one of Aspects 13 or 14, wherein the nitrification inhibitor comprises dimethylpyrazole 3,4-phosphate (DMPP), thiourea (TU), dicyandiamide ( DCD), 2-chloro-6-(trichloromethyl)-pyridine (epichloroidine), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (Edric) , 2-amino-4-chloro-6-methyl-pyrimidine (AM), 2-mercapto-benzothiazole (MBT) or 2-sulfathiazole (ST), or any combination thereof, preferably DCD. Aspect 16 relates to the fertilizer blend of any one of Aspects 1-15, wherein the core further comprises a plasticizer in an amount of 0.01 wt % to 5 wt %, based on the total weight of the core. Aspect 17 relates to the fertilizer blend of Aspect 16, wherein the plasticizer comprises hydroxypropyl methylcellulose (HPMC), carboxymethylcellulose, polyethylene glycol (PEG), guar gum, locust locust Soybean gum, xanthan gum, natural gum, lignosulfonate or hydroxyethyl cellulose or any combination thereof, preferably HPMC. Aspect 18 relates to the fertilizer admixture of any one of Aspects 1 to 17, wherein the core further comprises filler in an amount of 1 wt % to 60 wt %, based on the total weight of the core. 19 based on aspect 18 aspects of fertilizer blend, wherein the filler comprises silicon dioxide, distillers dried grains with solubles (DDGS), CaCO _3, chalk, or rice hulls, or any combination thereof. Aspect 20 pertains to a method of fertilizing, the method comprising applying the fertilizer blend of any one of Aspects 1 to 19 to soil, a crop, or at least a portion of a soil and a crop.

Other objects, features and advantages of the present invention will become apparent from the following drawings, embodiments and examples. It should be understood, however, that the drawings, implementations, and examples, while indicating specific embodiments of the invention, are given by way of illustration only, and are not intended to limit the invention. In addition, changes and modifications within the spirit and scope of the invention will be apparent to those skilled in the art upon careful consideration from this embodiment. In other embodiments, features from certain embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In other embodiments, additional features may be added to the specific embodiments described herein.

Cross-references to related applications

This application claims the benefit of priority from US Provisional Application No. 62/983,166, filed on February 28, 2020, which is incorporated herein by reference in its entirety.

The fertilizer blends of the present invention may contain a blend of at least two different granular fertilizer compositions (a first granular fertilizer composition and a second granular fertilizer composition). The first granular fertilizer composition can have a fertilizer particle comprising at least two discrete portions: a core having an outer surface, and a shell in contact with at least a portion of the outer surface of the core. The core may contain binders, pH buffers, urease inhibitors, and optionally nitrification inhibitors, plasticizers, and/or fillers. The shell may contain urea. The second granular fertilizer composition may contain plant fertilizers other than urea. In one aspect, the fertilizer admixture can be a dry fertilizer admixture (eg, a dry mixture comprising a plurality of first and second fertilizer particles).

These and other non-limiting aspects of the invention are discussed in further detail in the following sections. A. Fertilizer blends

The fertilizer blend of the present invention may contain i) 10% to 90% by weight, or at least, equal to, or between 10%, 15%, 20%, 25%, 30%, 35% by weight , 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, and 90 wt% of any two The first granular fertilizer composition between, and ii) 10% to 90% by weight, or at least, equal to, or between 10%, 15%, 20%, 25%, 30%, 35% by weight %, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, and 90% by weight The second granular fertilizer composition in between. The first and second granular fertilizer compositions may each include a plurality of particles, for example, the first fertilizer composition may include a plurality of the aforementioned core-shell particles, and the second fertilizer composition may include a plurality of the second fertilizer particles ; The admixture may comprise a mixture of a plurality of core-shell particles and a second fertilizer particle. The fertilizer blend can be a homogeneous or heterogeneous blend of the first granular fertilizer composition and the second granular fertilizer composition.

As illustrated in Figure 1, according to one example of the present invention, the granules of the first granular fertilizer composition may have a core-shell structure. FIG. 1 shows a cross-sectional view of a core-shell particle 10 . The core-shell particles may contain a core 2 and a shell 4 . Although the shape of the core-shell particles 10 is depicted as spherical, other shapes (eg, cylindrical, puck-shaped, oval, rectangular, etc.) are contemplated. The overall shape of the core-shell particle can be affected by the shape of the unskinned core (eg, spherical, cylindrical, puck, elliptical, elliptical, etc. cores can result in particles of a similar shape to the skin). The outer shell 4 can cover at least a part of the outer surface 2a of the core 2 . Although for the core-shell particle 10 depicted in Figure 1, the shell 4 covers the entire outer surface of the core 2, within the context of the present invention, the shell 4 can be easily fabricated and considered carefully to cover the outer surface of the core 2 A portion of 2a core-shell fertilizer particles (e.g., may cover 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99%). The core-shell structure of the granules of the first granular fertilizer composition is at least partially maintained in the fertilizer blend. Although the core-shell particle 10 depicted in Figure 1 contains one core 2, core-shell particles containing two or more cores can be readily fabricated.

Core 2 may contain binders, pH buffers and urease inhibitors. In some aspects, the core may contain from 10% to 95% by weight, or at least, equal to, or between 10%, 15%, 20%, 25%, 30% by weight, based on the total weight of the core %, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight and 95% by weight of the binder between any two. In some aspects, the core may contain from 5% to 60% by weight, or at least, equal to, or between 5%, 10%, 15%, 20%, 25% by weight, based on the total weight of the core %, 30 wt %, 35 wt %, 40 wt %, 45 wt %, 50 wt %, 55 wt %, and 60 wt % pH buffer. In some aspects, the core may contain from 0.1% to 5% by weight or from 1% to 5% by weight, or at least, equal to, or between 0.1%, 0.5%, 1% by weight, based on the total weight of the core %, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, and 5% by weight of any between urease inhibitor. The core may optionally contain plasticizers, nitrification inhibitors and/or fillers. In some aspects, the core may contain from 0.01 wt% to 5 wt%, or at least, equal to, or between 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.5 wt%, based on the total weight of the core %, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, and 5 wt% plasticizer in between any two. In some aspects, the core may contain from 10% to 30% by weight, or at least, equal to, or between 10%, 15%, 20%, 25%, and 30% by weight, based on the total weight of the core % of nitrification inhibitors in between. In some aspects, the core may contain from 1 wt% to 60 wt%, or at least, equal to, or between 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, based on the total weight of the core %, 25%, 30%, 35%, 40%, 45%, 50%, 55%, and 60% by weight of filler in between any two.

The casing 4 may contain urea. In some aspects, the shell 4 may contain from 50% to 100% by weight, or at least, equal to, or between 50%, 55%, 60%, 65%, 70% by weight, based on the total weight of the shell. Urea in between any of wt %, 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, and 100 wt %.

In addition to urea, the second granular fertilizer composition may also contain from 50% to 100% by weight, or at least, equal to, or between 50%, 55%, 60%, 65%, 70%, 75% by weight Additional plant fertilizers between any of wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, and 100 wt %. In some aspects, in addition to urea, the second granular fertilizer composition may also contain two or more additional plant fertilizers. In some specific aspects, the second granular fertilizer composition may comprise granules containing two or more additional plant fertilizers. In some specific aspects, the two or more additional plant fertilizers can be included in the second granular fertilizer composition in the form of two or more types of granules.

In some specific aspects, the second granular fertilizer composition can contain MAP, based on the total weight of the fertilizer blend, and the fertilizer blend can contain 30% to 70% by weight, or at least, equal to, or between 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, and 70 wt% of the first granular fertilizer composition , and 30% by weight to 70% by weight, or at least, equal to, or between 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight and 70 wt% MAP in between any two. The first granular fertilizer composition may include core-shell particles, and the core contains from 30% to 50% by weight, or at least, equal to, or between 30%, 35%, 40% by weight, based on the total weight of the core. %, 45%, and 50% by weight of plaster of paris, 5% to 20% by weight, or at least, equal to, or between 5%, 10%, 15%, and 20% by weight % Bleached wheat flour between any two, 30% to 55% by weight, or at least, equal to, or between 30%, 35%, 40%, 45%, 50%, and 55% by weight pH buffer (such as chalk) between any two in wt%, 1 wt% to 5 wt%, or at least, equal to, or between 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt% , 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, and 5 wt % of any between urease inhibitors (such as NBPT), 0.01 wt % to 2 wt%, or at least, equal to, or between 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, and 2 wt% A plasticizer (such as HPMC) in between any two, and based on the total weight of the shell, the shell contains 90% to 100% by weight, or at least, equal to, or between 50%, 55%, Any between 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and 100% by weight of urea.

In some specific aspects, the second granular fertilizer composition may contain MOP and MAP, and the fertilizer blend may contain i) 10 wt% to 50 wt%, or at least, equal to, based on the total weight of the fertilizer blend , or between 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, and 50% by weight of the first particle Fertilizer composition, ii) 30% to 70% by weight, or at least, equal to, or between 30%, 35%, 40%, 45%, 50%, 55%, 60%, MAP between any of 65 wt% and 70 wt%, and iii) 5 wt% to 50 wt%, or at least, equal to, or between 5 wt%, 10 wt%, 15 wt%, 20 wt% %, 25%, 30%, 35%, 40%, 45%, and 50% by weight of the MOP. The first granular fertilizer composition may include core-shell particles, and the core contains from 30% to 50% by weight, or at least, equal to, or between 30%, 35%, 40% by weight, based on the total weight of the core. %, 45%, and 50% by weight of plaster of paris, 5% to 20% by weight, or at least, equal to, or between 5%, 10%, 15%, and 20% by weight % Bleached wheat flour between any two, 30% to 55% by weight, or at least, equal to, or between 30%, 35%, 40%, 45%, 50%, and 55% by weight pH buffer (such as chalk) between any two in wt%, 1 wt% to 5 wt%, or at least, equal to, or between 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt% , 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, and 5 wt % of any between urease inhibitors (such as NBPT), 0.01 wt % to 2 wt%, or at least, equal to, or between 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, and 2 wt% A plasticizer (such as HPMC) in between any two, and based on the total weight of the shell, the shell contains 90% to 100% by weight, or at least, equal to, or between 50%, 55%, Any between 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and 100% by weight of urea.

In some specific aspects, the second granular fertilizer composition may contain ammonium sulfate, and the fertilizer blend may contain 50% to 90% by weight, or at least, equal to, or between 50% by weight, based on the total weight of the fertilizer blend. %, 55%, 60%, 65%, 70%, 75%, 80%, 85%, and 90% by weight of the first granular fertilizer composition, and 10 wt% to 50 wt%, or at least, equal to, or between any two of 30 wt%, 35 wt%, 40 wt%, 45 wt%, and 50 wt% ammonium sulfate. The first granular fertilizer composition may include core-shell particles, and the core contains from 30% to 50% by weight, or at least, equal to, or between 30%, 35%, 40% by weight, based on the total weight of the core. %, 45%, and 50% by weight of plaster of paris, 5% to 20% by weight, or at least, equal to, or between 5%, 10%, 15%, and 20% by weight % Bleached wheat flour between any two, 30% to 55% by weight, or at least, equal to, or between 30%, 35%, 40%, 45%, 50%, and 55% by weight pH buffer (such as chalk) between any two in wt%, 1 wt% to 5 wt%, or at least, equal to, or between 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt% , 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, and 5 wt % of any between urease inhibitors (such as NBPT), 0.01 wt % to 2 wt%, or at least, equal to, or between 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, and 2 wt% A plasticizer (such as HPMC) in between any two, and based on the total weight of the shell, the shell contains 90% to 100% by weight, or at least, equal to, or between 50%, 55%, Any between 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and 100% by weight of urea.

In some aspects, the urease inhibitor can include triamide phosphorothioate derivatives, and/or phenylphosphonium diamide (PPDA). In some aspects, the triamide phosphorothioate derivative can be triamide N-(n-butyl) phosphorothioate (NBPT), and/or triamide N-(n-propyl) phosphorothioate (NPPT). In some aspects, the urease inhibitor can include NBPT.

In some aspects, pH buffers may _{CaCO 3, MgO, KH 2 PO} 4, NaHCO 3, aluminum hydroxide, magnesium hydroxide, aluminum / magnesium hydroxide co-precipitate, aluminum hydroxide / sodium bicarbonate coprecipitate Calcium acetate, calcium bicarbonate, calcium borate, calcium carbonate, calcium bicarbonate, calcium citrate, calcium gluconate, calcium hydroxide, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate , magnesium acetate, magnesium borate, magnesium bicarbonate, magnesium carbonate, magnesium hydroxide, magnesium lactate, magnesium oxide, magnesium phosphate, magnesium silicate, magnesium succinate, magnesium tartrate, potassium acetate, potassium carbonate, potassium bicarbonate, potassium borate , potassium citrate, potassium metaphosphate, potassium phthalate, potassium phosphate, potassium polyphosphate, potassium pyrophosphate, potassium succinate, potassium tartrate, sodium acetate, sodium bicarbonate, sodium borate, sodium carbonate, sodium citrate, Sodium gluconate, disodium hydrogen phosphate, sodium hydroxide, sodium lactate, sodium phthalate, sodium phosphate, sodium polyphosphate, sodium pyrophosphate, sodium tartrate, sodium tripolyphosphate, synthetic hydrotalcite, tetrapotassium pyrophosphate, pyrophosphate Tetrasodium, tripotassium phosphate, trisodium phosphate, and tromethamine, and combinations thereof. In some aspects, the pH buffering agent can be CaCO _3. In some aspects, the chalk CaCO ₃ as included therein.

In some aspects, the filler may contain one or more of the following: silicon dioxide, distillers dried grains with solubles _{(DDGS), CaCO 3, MgO} , CaO, bone meal or rice hulls, or a mixture thereof. Other suitable fillers known in the art may also be used. In some aspects, pH buffers can also act as fillers. For example, in some aspects, CaCO ₃ as a filler and as a pH buffer. In some cases, in addition to CaCO _3, no other filler or pH buffering agents included in the core particle.

In some aspects, the nitration inhibitor can include dimethylpyrazole 3,4-phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-(trichloromethyl) -pyridine (epichloropyridine), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (edari), 2-amino-4-chloro-6-methyl- Pyrimidine (AM), 2-mercapto-benzothiazole (MBT) or 2-sulfathiazole (ST), or any combination thereof, preferably DCD.

In some aspects, the plasticizer can be hydroxypropylmethylcellulose (HPMC), carboxymethylcellulose, hydroxyethylcellulose, polyethylene glycol (PEG), guar gum, locust bean gum, Xanthan gum, other natural gums, synthetic polymers based on acrylates, polyacrylamide (PAM), PVP, combinations of synthetic polymers, or carbomers, any combination thereof, preferably HPMC.

In some aspects, in addition to urea, the second specific fertilizer composition may also contain a plant fertilizer. In some aspects, the second particular fertilizer composition can include a source of phosphorus (P), a source of nitrogen (N) other than urea, a source of potassium (K), a source of nitrogen and phosphorus (NP), a source of phosphorus and potassium (PK) ), nitrogen, phosphorus and potassium (NPK) sources, micronutrients, calcium sources, sulfur sources, or any combination thereof. In some aspects, the micronutrients can include phytologically acceptable forms of inorganic or organometallic compounds, such as boron, copper, iron, chloride, manganese, molybdenum, nickel, and/or zinc. In some aspects, the second specific fertilizer composition can contain ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), potassium dihydrogen phosphate (MKP), triple superphosphoric acid Calcium (TSP), Rock Phosphate, Single Superphosphate (SSP) or any combination thereof. In some aspects, the second specific fertilizer composition may further include urea.

A number of urease inhibitors have been developed to enhance the efficiency of urea fertilizers. However, due to stability issues with some of these urease inhibitors under various conditions (such as pH, temperature, precipitation, presence of additional fertilizer components other than urea, etc.), the application of these urease inhibitors Can be challenging. For example, NBPT is known to be a good inhibitor of urease, but it is unstable at acidic pH. NBPT also decomposes when directly exposed to high temperatures, such as the temperature at which urea melts (about 135 to 140°C). In the case of nitrogenous fertilizers, the soil environment can become acidic after application. Therefore, urease inhibitors that are sensitive to acidic pH degrade and will not achieve their full performance. Including large excesses of urease inhibitors to compensate for losses due to pH changes may not be successful because fertilizers present in large excess (compared to the urease inhibitors) continue to alter the pH of the soil environment. Also, based on specific needs (such as soil type, climate, or other growing conditions), additional fertilizers other than urea, along with urea, are used to maximize plant growth and crop yield. NBPT can also be decomposed in the presence of other plant fertilizers in addition to urea. Without wishing to be bound by theory, the fertilizer blends of the present invention may provide solutions to at least some of these problems. The shell of the core-shell particle can protect the urease inhibitor in the core of the core-shell particle from additional plant fertilizers in the second granular fertilizer composition. In addition, the binder and pH buffer in the core and the urea in the shell protect the urease inhibitor from degradation during manufacture of the core (eg, protection from high temperature, high pressure, acidic pH conditions, etc.). The pH buffer can neutralize the acidity caused by urea hydrolysis, thereby preventing degradation of the urease inhibitors, such as, for example, NBPT when placed in soil with an acidic pH. Thus, the pH buffer can increase the effectiveness of urease inhibitors (eg, NBPT) and also maintain soil pH. In some aspects, certain pH buffers may also act as heat shielding materials for other components in the core, such as NBPT, and as fillers. For example, in some embodiments, CaCO ₃ pH buffering agents and fillers may be used and may improve the physical properties of the core, such as compression strength, and homogeneity of the inhibitory agent from the core particle release kinetics. The plasticizer can promote the desired continuous and uniform flow characteristics of the mixture used to form the core.

The fertilizer admixture granules of the present invention, such as the first granular fertilizer composition granules and/or the second granular fertilizer composition granules, can have desired physical properties, such as desired levels of abrasion resistance, granule strength, granulability Properties, hygroscopicity, particle shape and particle size distribution are all important properties of fertilizers.

The fertilizer blends described herein can be included in compositions suitable for application to soil. In addition to the fertilizer blend, the composition may also include other fertilizer compounds, micronutrients, macronutrients, additional urea, additional nitrogen nutrients, pesticides, herbicides or fungicides, or combinations thereof. B. Method of making fertilizer granules

The fertilizer blends of the present invention can be obtained by mixing 1:9 to 9:1, or at least, equal to, or between 1:9, 2:8, 3:7, 4:6, 5:5, 6:4 , 7:3, 8:2 and 9:1 in a weight ratio between any two of the first granular fertilizer composition and the second granular fertilizer composition are formed by blending. The first granular fertilizer composition and the second granular fertilizer composition can be blended by methods known in the art. For example, the first granular fertilizer composition and the second granular fertilizer composition may be blended by dry blending in granular form. In some aspects, a first granular fertilizer composition in granular form can be contacted with a second granular fertilizer composition in granular form and can be mixed to form the fertilizer blend. The first granular fertilizer composition and the second granular fertilizer composition can be blended, for example, in an apparatus such as a blender known in the art.

The first granular fertilizer composition can be formed by forming a core having an outer surface, contacting at least a portion of the outer surface of the core with a urea-containing solution or urea melt, and cooling and/or drying the outer surface of the core At least a portion of the contacted urea solution or urea melt forms a shell. The core may be formed by granulating, compacting, and/or extruding a composition containing core ingredients such as binders, pH buffers, urease inhibitors, and optionally plasticizers, fillers, and/or nitrification inhibitors form.

In some aspects, the granulation process for core formation can include forming a powdered composition containing the core ingredients and extruding the powdered composition through a die to form a granulated core having a desired shape. The pelletizing process can be carried out using pelletizing presses known in the art. In some aspects, the core ingredients can be mixed in a mixer, such as a turbine mixer, to form a powdered composition from which the powdered composition can be fed to a granulation press connected to The screw feeder. In some aspects, the powdered composition can be fed to the screw feeder at a rate of 40 kg/hr to 100 kg/h, or 50 kg/hr to 80 kg/h. In some aspects, the pelletizing press can include twin rolls rotating at a speed of 150 to 200 RPM, and the powdered composition can be extruded through the die by the rolls.

In some aspects, the compaction process of core formation can include forming a powdered composition by mixing the core ingredients in dry form, compacting the powdered composition to form a compacted composition, and crushing, grinding and/or Or granulate the compacted composition to form cores of the desired shape and size. The compaction process can be carried out using roller presses known in the art. In some aspects, the powdered composition can be compacted by feeding the powdered composition into a roll press containing a rotating roll and a roll of a stationary phase, and forming flakes from the powdered composition Form of compacted composition.

In some aspects, the extrusion process for core formation can include forming an extrudable composition containing the core components, and extruding the extrudable composition. The method may also include a drying step after extrusion to remove solvent that may have been added to make the composition extrudable. In some aspects, the extrudable composition can be formed from the core ingredients in dry form, with the addition of any solvent as desired. In some aspects, the solvent can be water. The extrusion can be carried out using a suitable extruder apparatus known in the art, and can be carried out at a temperature between 0°C and 150°C and a screw speed of 1 to 500 rpm, wherein the extruder comprises a A multi-feeder containing extrusion components including main drives, shafts, screws, barrels and/or dies.

The core can then be contacted with a urea solution or molten urea to form a urea-based shell, thereby forming a first granular fertilizer composition comprising core-shell fertilizer particles. The contacting can include between 100°C and 145°C, or at least, equal to, or between 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, and 145°C The urea solution or urea melt is sprayed onto the core particles at any temperature in between. When the urea solution or urea melt is sprayed onto the core particles, it can be cooled and dried to form a solidified skin or shell on at least a portion of the outer surface of the core, which can result in the core-shell of the present invention Fertilizer Granules. The resulting fertilizer granules can be of various sizes and shapes. In some aspects, the urea solution may contain from 80% to 98% by weight, or at least, equal to, or between 80%, 95%, 90%, 91%, 92%, 93% by weight %, 94% by weight, 95% by weight, 96% by weight, and 98% by weight of urea in aqueous urea solution. C. Method of using fertilizer granules

The fertilizer blends of the present invention can be used in methods of increasing the amount of i) nitrogen and, if desired, ii) phosphorus and/or potassium in soil, and enhancing plant growth. Such methods may include applying to soil an effective amount of a composition comprising the fertilizer admixture of the present invention. The method can include increasing the growth and yield of crops, trees, ornamental plants, etc., such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and soybeans. The method can include applying the fertilizer blend of the present invention to at least one of soil, organism, liquid carrier, liquid solvent, and the like.

Non-limiting examples of plants that may benefit from the fertilizers of the present invention include vines, trees, shrubs, stem plants, ferns, and the like. Such plants may include orchard crops, vines, ornamental plants, food crops, timber and harvested plants. Such plants may include gymnosperms, angiosperms and/or ferns. Such gymnosperms may include those from the families Araucariaceae, Cupressaceae, Pinaceae, Podocarpaceae, Sciadopitaceae, Taxaceae, Cycadaceae ) and plants of the Ginkgoaceae family. The angiosperms may include those from the family Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae ( Araliaceae), Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bigoniaceae, Bombacaceae, Violet Boraginaceae, Burseraceae, Buxaceae, Canellaceae, Cannabaceae, Capparidaceae, Caprifoliaceae, Caricaceae , Casuarinaceae, Celastraceae, Cercidiphyllaceae, Chrysobalanaceae, Clusiaceae, Combretaceae, Cornaceae ), Cyrillaceae, Davidsoniaceae, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Butterflyaceae (Fabaceae), Fagaceae, Grossulariaceae, Hamamelidaceae, Hippocastanaceae, Illiciaceae, Juglandaceae, Lauraceae ), Lecythidaceae, Lythraceae, Magnoliaceae, Malpighiaceae, Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringaceae, Muntingiaceae, Myoporaceae, Myricaceae, Myrsin family), Myrtaceae, Nothofagaceae, Nyctaginaceae, Nyssaceae, Olacaceae, Oleaceae, Oleaceae (Oleaceae) Oxalidaceae), Pandanaceae, Papaveraceae, Phyllanthaceae, Pittosporaceae, Platanaceae, Poaceae, Polygonaceae , Proteaceae, Punicaceae, Rhamnaceae, Rhizophoraceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae ), Sapindaceae, Sapotaceae, Simaroubaceae, Solanaceae, Staphyleaceae, Sterculiaceae, Strelitziaceae, Benzoin Styracaceae, Surianaceae, Symplocaceae, Tamaricaceae, Theaceae, Theophrastaceae, Thymelaeaceae, Tiliaaceae (Tiliaceae), Ulmaceae (Ulmaceae), Verbenaceae (Verbenaceae), and/or Vitaceae (Vitaceae).

The effectiveness of a composition comprising the fertilizer admixture of the present invention can be determined by measuring the amount of nitrogen in the soil at various times after the fertilizer composition is applied to the soil. It should be understood that different soils have different properties that can affect the stability of nitrogen in that soil. The effectiveness of fertilizer compositions can also be compared directly to other fertilizer compositions by making a side-by-side comparison in the same soil under the same conditions.

In one aspect, the fertilizer admixtures of the present invention may contain particles that are denser than water. This allows the particles to sink in the water instead of floating. This may be particularly advantageous where application to crops that are at least partially or fully submerged in water is contemplated. A non-limiting example of such a crop is rice, as the land in a rice field is usually submerged in water. Thus, the application of the fertilizer blend to these crops can be carried out such that the fertilizer blend particles are evenly distributed over the submerged land. By comparison, particles that are less dense than water will tend to remain in or on the water surface, which can result in the particles being washed away and/or the particles agglomerating, neither of which can achieve homogenization of the particles. Distributed on the ground submerged in water. Example

The invention will be described in more detail with the aid of specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize various non-critical parameters that can be changed or modified to produce substantially the same results. Example 1 Fertilizer Blend Preparation

Comparative Fertilizer Blend Preparation. Comparative fertilizer blends containing i) urease inhibitor-coated urea granules having a urease-containing core and a urease inhibitor-containing skin layer, wherein the skin layer covers the core, were prepared using the following method. at least a portion of the outer surface, and ii) a second granular fertilizer composition containing additional plant fertilizers in addition to urea. The urease inhibitor coated urea was prepared in a batch process using a drum coating system. The drum coating system has a capacity of 200 grams to 2 kg, and a drum interchange facility based on the required volume. The drum included four baffles, each 0.5 inch in height and 1 inch in width, over the entire length of the drum, which aided in mixing the urea granules. The drum coater system works in manual mode, starting from feeding, to pumping, spraying, discharging, drying and discharging the coated material. Solutions containing inhibitors were obtained from commercial sources and used to coat granular urea in the range of 2 to 3 liters per ton of urea. Initially, the desired amount of screened (> 2.00 mm and < 4.00 mm) granular urea product is weighed and fed into the drum. The coating solution was pumped using a peristaltic pump. The pump is connected to a nozzle that uses compressed air to atomize the spray. A vent line was placed on top of the drum to remove the compressed air. After spraying the coating solution was complete, the pump was stopped and the drum rotation continued for another five minutes to ensure dispersion of the coating. The product is then collected for packaging. The process parameters are provided below. The inhibitor-coated urea was blended with other fertilizers such as monoammonium sulfate (MAP), potassium chloride (MOP), and ammonium sulfate (AS) to make comparative fertilizer blends 5-8. The individual components of the blends were weighed and mixed in a zip lock lid. Table 1 shows the compositions of Comparative Fertilizer Blends 5-8.

Process parameters: Drum RPM : 20 Spray speed : 02 ml/min Nozzle Type : Orifice Distance from nozzle to coating bed: 300 to 600 mm Atomizing air pressure : 0.1 bar

Fertilizer blend preparation. Use the following method to prepare fertilizer blends containing i) a first granular fertilizer composition containing core-shell fertilizer granules having a core containing a urease inhibitor and a shell containing urea, wherein the shell covers the at least a portion of the outer surface of the core, and ii) a second granular fertilizer composition containing additional plant fertilizers other than urea. The composition containing plaster of paris, bleached wheat flour, chalk, NBPT and HPMC was formed into core agglomerates by extrusion. The core has an average diameter of 0.7 to 1.7 mm. Based on total weight of the core, the core contains 40.39% by weight of the plaster, 47.32% by weight of the chalk / CaCO _3, 9.79% by weight of bleached wheat flour, 2.2% of the weight of NBPT, and 0.3% by weight of HPMC.

Process parameters: Feed rate: 10 kg/hr. Screw RPM: 200 to 250. Temperature: room temperature. Output torque: 11 to 30 Nm.

The cores produced as above were coated with an aqueous urea melt solution (90 to 96% urea) in a granulator. The solution is then dried to form a solidified urea shell on the outer surface of the core agglomerates to form core-shell particles. The temperature of the pelletizing machine is 80°C to 110°C. The core-shell particles are dry blended with fertilizers such as monoammonium sulfate (MAP), potassium chloride (MOP), and ammonium sulfate (AS) to prepare fertilizer blends 1-4. The individual components are weighed and mixed in a zip lock lid. Table 1 shows the composition of Fertilizer Blends 1-4. MAP and AS were obtained from Kynoch, and MOP was obtained from the local Indian market. Table 1: Different fertilizer blends prepared blend Component weight % Inhibitor-coated urea core-shell particles MAP MOP AS Fertilizer Blend 1 - 20 50 30 0 Fertilizer Blend 2 - 37 52 11 0 Fertilizer Blend 3 - 50 50 0 0 Fertilizer Blend 4 - 75 0 0 25 Compare Fertilizer Blends 5 20 - 50 30 0 Compare Fertilizer Blends 6 37 - 52 11 0 Compare Fertilizer Blends 7 50 - 50 0 0 Compare Fertilizer Blends 8 75 - 0 0 25 Example 2 Urease Stability in Fertilizer Blends

Method: Inhibitor stability was monitored in blended samples under two different storage conditions, a) at room conditions, and b) at 40 ± 2°C and 75 ± 5% relative humidity. Fertilizer granules from different blends were carefully selected at different time intervals (as shown in Tables 2 to 4) and the urease inhibitor NBPT was quantified using HPLC techniques. Unblended core-shell particles and inhibitor-coated urea samples were used as control samples. Table 2: Percent recovery of NBPT in blended samples stored at room conditions. sample Day 0 Day 7 Day 14 Fertilizer Blend 3 100 79.4 65.8 Fertilizer Blend 4 100 73.7 62.4 Compare Fertilizer Blends 7 100 56.9 15.5 Compare Fertilizer Blends 8 100 34.2 43.2 Table 3: Percent recovery of NBPT in blended and control samples stored at room conditions. sample Day 0 Day 3 Day 14 Day 31 Day 60 core-shell particles 100 98.2 100.9 91.8 100.0 Fertilizer Blend 1 100 89.1 44.5 27.3 11.8 Fertilizer Blend 2 100 95.5 43.6 30.0 9.1 Inhibitor-coated urea 100 101.0 100.0 94.1 96.0 Compare Fertilizer Blends 5 100 88.1 18.8 2.0 0.0 Compare Fertilizer Blends 6 100 89.1 15.8 0.0 0.0 Table 4: Percent recovery of NBPT in blended and control samples stored at 40 ± 2°C and 75 ± 5% relative humidity. sample Day 0 Day 1 Day 15 Day 30 core-shell particles 100 101.8 94.5 85.5 Fertilizer Blend 1 100 52.7 7.3 0.0 Fertilizer Blend 2 100 48.2 4.5 0.0 Inhibitor-coated urea 100 102.0 97.0 86.1 Compare Fertilizer Blends 5 100 19.8 0.0 0.0 Compare Fertilizer Blends 6 100 19.8 0.0 0.0

Results: Tables 3 and 4 show that NBPT is more stable in unblended samples (eg, core-shell particles and inhibitor-coated urea) compared to blended samples, indicating that NBPT is more stable in addition to urea Degrades in the presence of fertilizers such as MAP, MOP and/or AS. The results presented in Tables 2-4 show that NBPT is more stable in Fertilizer Blends 1-4 compared to Comparative Fertilizer Blends 5-8. For example, Fertilizer Blend 1 and Comparative Fertilizer Blend 5 contained similar weight % MAP and MOP. Fertilizer Blend 1 had a higher NBPT recovery rate indicating NBPT stability than Comparative Fertilizer Blend 5 when stored at room conditions or at 40 ± 2°C and 75 ± 5% relative humidity. For example, when stored under room conditions for 31 days, the NBPT recovery for Fertilizer Blend 1 was 27.3%, while under the same conditions, only 2% NBPT recovery was observed for Comparative Fertilizer Blend 5. For Fertilizer Blend 2 compared to Comparative Fertilizer Blend 6 (containing similar wt % MAP and MOP), Fertilizer Blend 3 compared to Comparative Fertilizer Blend 7 (containing similar wt % MAP), and Similar trends in NBPT recovery were also observed for Fertilizer Blend 4 compared to Comparative Fertilizer Blend 8 (containing similar wt % AS).

2: Core 2a: outer surface 4: Shell 10: Core-Shell Particles

Those skilled in the art will appreciate the advantages of the present invention with the benefit of the following embodiments and upon reference to the accompanying drawings. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown in the drawings by way of example. The drawings may not be drawn to scale.

Figure 1 illustrates a cross-section of a core-shell particle of a first granular fertilizer composition according to an example of the present invention.

2: Core

2a: outer surface

4: Shell

10: Core-Shell Particles

Claims (20)

A fertilizer blend comprising: 10% to 90% by weight of the first granular fertilizer composition comprising a core and a shell, the core comprising a binder, a pH buffer and a urease inhibitor, and the shell comprising urea, wherein the shell covers the outer surface of the core at least a portion; and 10% to 90% by weight of the second granular fertilizer composition, wherein the second granular fertilizer composition is blended with the first granular fertilizer composition. The fertilizer blend of claim 1, wherein the second granular fertilizer composition comprises ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP), potassium dihydrogen phosphate (MKP) , triple superphosphate (TSP), phosphate rock, single superphosphate (SSP), or any combination thereof. The fertilizer blend of claim 1 or 2, wherein the second granular fertilizer composition comprises MAP and MOP, and the fertilizer blend comprises 10% to 50% by weight of the first granular fertilizer composition, 30% by weight % to 70 wt% of MAP and 5 to 50 wt% of MOP. The fertilizer blend of any one of claims 1 or 2, wherein the second granular fertilizer composition comprises MAP, and the fertilizer blend comprises 30% to 70% by weight of the first granular fertilizer composition, and 30% to 70% MAP by weight. The fertilizer blend of any one of claims 1 or 2, wherein the second granular fertilizer composition comprises ammonium sulfate, and the fertilizer blend comprises 50% to 90% by weight of the first granular fertilizer composition , and 10% to 50% by weight of ammonium sulfate. The fertilizer blend of any one of claims 1 or 2, wherein the binder comprises plaster of paris, flour, bleached wheat flour, starch, gluten, kaolin, bentonite, or colloidal silica or any combination thereof, preferably Gypsum of paris and/or bleached wheat flour. The requested item 1 or 2 fertilizer blend according to any one of, wherein the pH buffer comprises _{CaCO 3, Na 2 CO 3,} K 2 CO 3, MgO, KH 2 PO 4, NaHCO 3 or MgCO _3, or any composition, preferably CaCO _3. The fertilizer blend of any of claims 1 or 2, wherein the urease inhibitor comprises a triamide thiophosphate derivative, preferably N-(n-butyl) triamide thiophosphate (NBPT) . The fertilizer blend of any of claims 1 or 2, wherein the binder is present in the core in an amount of 10% to 95% by weight, based on the total weight of the core. The fertilizer blend of any one of claims 1 or 2, wherein the pH buffering agent is present in the core in an amount of 5% to 60% by weight, based on the total weight of the core. The fertilizer blend of any one of claims 1 or 2, wherein the urease inhibitor is present in the core in an amount of 1 wt% to 5 wt% based on the total weight of the core. The fertilizer blend of any of claims 1 or 2, wherein the outer shell comprises 50% to 100% by weight, preferably 85% to 100% by weight of urea, based on the total weight of the outer shell. The fertilizer blend of any of claims 1 or 2, wherein the core further comprises a nitrification inhibitor. The fertilizer blend of claim 13, wherein the nitrification inhibitor is present in the core in an amount of 10% to 30% by weight, based on the total weight of the core. The fertilizer blend of claim 13, wherein the nitrification inhibitor comprises dimethylpyrazole 3,4-phosphate (DMPP), thiourea (TU), dicyandiamide (DCD), 2-chloro-6-( Trichloromethyl)-pyridine (Nitrapyrin), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (Terrazole), 2-amine yl-4-chloro-6-methyl-pyrimidine (AM), 2-mercapto-benzothiazole (MBT) or 2-Sulfanimalamidothiazole (ST), or any combination thereof, preferably DCD. The fertilizer blend of any of claims 1 or 2, wherein the core further comprises a plasticizer in an amount of 0.01 wt% to 5 wt%, based on the total weight of the core. The fertilizer blend of claim 16, wherein the plasticizer comprises hydroxypropyl methylcellulose (HPMC), carboxymethylcellulose, polyethylene glycol (PEG), guar gum, locust bean gum, yellow Original gum, natural gum, lignosulfonate or hydroxyethyl cellulose or any combination thereof, preferably HPMC. The fertilizer admixture of any of claims 1 or 2, wherein the core further comprises fillers in an amount of 1 wt% to 60 wt% based on the total weight of the core. The requested item 18 of the fertilizer blend, wherein the filler comprises silicon dioxide, distillers dried grains with solubles (DDGS), CaCO _3, chalk, or rice hulls, or any combination thereof. A method of fertilizing, the method comprising applying the fertilizer blend of any one of claims 1 to 19 to soil, a crop, or at least a portion of the soil and the crop.

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